Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
  • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
  • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/72—Two oxygen atoms, e.g. hydantoin
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D249/12—Oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
  • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
  • C07D253/06—1,2,4-Triazines
  • C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
  • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D253/075—Two hetero atoms, in positions 3 and 5
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
  • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D257/04—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems

Definitions

• This invention pertains to novel herbicidal 2-[(4-heterocyclic-substituted-3-halophenoxymethyl)phenoxy]-alkanoates, especially propionates and acetates, and their use for weed control in agriculture, horticulture, and other fields in which it is desired to control unwanted plant growth, such as grassy or broad-leaf plant species.
• heterocyclic moiety is selected from among 4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-on-1-yl, 3,4,5,6-tetrahydro-phthalimid-1-yl, 1-(1-methylethyl)imidazolidin-2,4-dion-3-yl, 1,4-dihydro-4-(3-fluoropropyl)-5H-tetrazol-5-on-1-yl, 3-chloro-4,5,6,7-tetrahydroindazol-2-yl, 4-methyl-1,2,4-triazine-3,5-dion-2-yl, 8-thia-1,6-diazabicyclo[4.3.0]nonane-7-on-9-ylimino, and 1-methyl-6-trifluoromethyl-2,4-pyrimidinedione-3-yl groups.
• R a is preferably lower haloalkyl
• R b is
• R' and R 2 are broadly defined;
• X and Y are independently halogen, alkyl, alkoxy, alkylthio, haloalkyl, nitro, cyano, sulfonylalkyl, or -SOCF 3 ;
• M is CH or N
• A is a derivative of an alkanoate bonded to the phenoxy oxygen at the alpha carbon.
• U.S. 4,816,065 discloses compounds like those of U.S. 5,084,085, except that the triazolinone ring has been replaced by a 3 ,4,5,6-tetrahydrophthalimido moiety.
• U.S. 4,885,025 discloses compounds in which the triazolinone ring of U.S. 5,084,085 has been replaced with a tetrazolinone moiety.
• X is hydrogen, halogen, nitro, alkyl, or alkoxy
• Y is hydrogen, halogen, alkyl
• n and m are each 1 to 4.
• Q is selected from the following heterocycles:
• W is oxygen or sulfur
• X is selected from hydrogen, methyl, fluorine, or chlorine
• Y is hydrogen, or
• X and Y taken together may be - ⁇ -C(CH 3 ) 2 CH 2 - to form a 7-substituted-4-benzofuranyl moiety;
• R' is hydrogen or methyl
• R" is -OR or amino, arylamino (e.g. phenylamino), alkylamino (e.g. lower alkylamino such as
• alkenylamino e.g. lower alkenylamino such as diallylamino
• alkoxyamino e.g. lower alkoxyamino such as methoxyamino
• cyano or alkyl-, haloalkyl-, or arylsulfonylamino of the formula -N(lower
• alkyl SO 2 R 9 , or -NHSO 2 R 9 ;
• R is hydrogen, M, alkyl (e.g., lower alkyl such as methyl or ethyl), cycloalkyl, lower alkenyl or lower alkynyl, each optionally substituted with one or more chlorine or fluorine, or
• each of R 1 through R 6 is lower alkyl or lower
• R 7 is hydrogen or lower alkyl
• R 8 is alkyl, preferably lower alkyl
• R 9 is alkyl (e.g. lower alkyl such as methyl, ethyl or propyl), haloalkyl (e.g. halo lower alkyl such as trifluoromethyl), or aryl such as phenyl or substituted phenyl, (e.g. lower alkoxy-substituted and/or halo-substituted phenyl);
• n is 1 to 6, preferably 1 to 3;
• M is a monovalent, salt-forming group such as
• Z is hydrogen, fluorine, chlorine, bromine, lower alkyl, phenyl, or methoxy
• Z' is hydrogen, fluorine, or chlorine; or Z and Z' taken together may be -(CH 2 ) 4 - to form a tetrahydronaphthyl moiety;
• the group A-O- may be in the 2, 3, or 4-position of the phenyl ring.
• Preferred compounds are those in which R" is -OR and Z is chlorine or lower alkyl.
• R is lower alkyl, lower chloroalkyl, or -[CHR 7 - (CH 2 ) m O] n R 8 ;
• R 1 is difluoromethyl;
• R 2 is methyl;
• R 3 is 1-methylethyl;
• R 4 is 3-fluoropropyl;
• R 5 is methyl;
• R 6 is methyl;
• R 7 is H or
• R' is methyl; Z is in the 4-position; Z' is hydrogen or chlorine in the 3-position; m is 0 or 1, and n is 1 to 3; and the group AO- is in the 2-position of the phenyl ring.
• the diazonium salt of 2-fluoro-4-methoxyaniline was prepared using sodium nitrite and hydrochloric acid and was then reduced in situ with tin (II) chloride to prepare the correspondingly substituted phenylhydrazine (XIX). Reaction of this hydrazine with ethyl 2-cyclohexanonecarboxylate and subsequent heating of the product in the presence of acetic acid produced a mixture of 2-(2-fluoro-4-methoxyphenyl)-4,5,6,7-tetrahydro-1H-indazol-3-one (XX) and the 2-fluoro-4-methoxyphenylhydrazone of 2-cyclohexanonecarboxylic acid.
• Reduction of the sulfonyl chloride moiety to a thiol group was effected using tin (II) chloride in acetic acid, yielding, for example, 4-(4- difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol- 5(1H)-on-1-yl)-3-fluorothiophenol (XXX), the desired intermediate.
• the compounds in which Q is 1-methyl-6-trifluoromethyl-2,4-pyrimidinedione-3-yl may be prepared by the method of Schema I through the preparation of XXXII. Then XXXII is converted to the isocyanate with phosgene in place of thiophosgene, and the isocyanate is reacted with ethyl 3-amino-4,4,4-trifluoro-2-butenoate to yield the desired herbicidal compound.
• lower alkyl contains 1 to 6 carbons, preferably 1 to 4
• lower alkenyl or “lower alkynyl” contains 2 to 6 carbons, preferably 2 to 4
• cycloalkyl contains 3 to 6 carbons
• halogen or “halo” means bromine, chlorine, or fluorine, preferably chlorine or fluorine.
• Step A 2-Fluoro-4-nitrophenylhydrazone of pyruvic
• Step C 1-(2-Fluoro-4-nitrophenyl)-4-difluoromethyl- 4,5-dihydro-1,2,4-triazol-5(1H)-one
• This mixture was extracted twice with diethyl ether. The combined extracts were washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure, leaving a dark brown solid residue. This solid was dissolved in 100 mL of acetic acid and 5 mL of hydrobromic acid, and this solution was heated at reflux for one hour. This mixture was poured over ice and was then extracted with ethyl acetate. This extract was washed twice with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure, leaving a black oil as a residue.
• Step D 1-(2-Fluoro-4-aminophenyl)-4-difluoromethyl- 4,5-dihydro-3-methyl-l, 2,4-triazol-5(1H)-one
• Step E 1-(2-Fluoro-4-hydroxyphenyl)-4-difluoromethyl- 4,5-dihydro-3-methyl-l,2,4-triazol-5(1H)-one
• a solution of 20.0 g (0.0774 mole) of 1-(2-fluoro-4-aminophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 100 mL of concentrated sulfuric acid was cooled to 15-20°C.
• a solution of 5.3 g (0.0774 mole) of sodium nitrite in 20 mL of water was added slowly to the sulfuric acid solution while the temperature was maintained between 15°C and 20°C.
• the extract was combined with the brown oil from the organic phase, and the solvent was evaporated under reduced pressure, again leaving a brown oil.
• This brown oil was placed on a silica gel column and eluted with methylene chloride/ethyl acetate (90/10).
• the product-containing fractions were combined, and the solvent was evaporated under reduced pressure, leaving 12.17 g of 1-(2-fluoro-4-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, m.p. 112-114°C.
• the NMR spectrum was consistent with the proposed structure.
• Step F Methyl 2-(formyl-5-methylphenoxy)propionate
• a mixture of 6.0 g (0.0441 mole) of 4-methylsalicylaldehyde, 7.31 g (0.0529 mole) of potassium carbonate, and 8.62 g (0.0529 mole) of methyl 2-bromopropionate in 50 mL of 2-butanone was heated at 70°C for approximately seventeen hours. The mixture was then filtered, and the filtrate was evaporated under reduced pressure, leaving a light yellow oil as a residue.
• Step G Methyl 2-(2-hydroxymethyl-5-methylphenoxy)- propionate To a solution of 7.89 g (0.0355 mole) of methyl 2-(2-formyl-5-methylphenoxy)propionate in 20 mL of methanol, cooled to 5°C, was added a solution of 0.10 g (0.0018 mole) of sodium methoxide in 20 mL of methanol. While the temperature was maintained between 0°C and 5°C, 0.36 g (0.0094 mole) of sodium borohydride was added to the reaction during a period of about 10 minutes. The reaction mixture was allowed to warm to ambient temperature, where it was stirred for two hours. At the end of this period, the reaction mixture was poured into 75 mL of 0.25 N hydrochloric acid.
• Step I Methyl 2-[2-[4-(4-difluoromethyl-4,5-dihydro- 3-methyl-1,2,4-triazol-5(1H)-on-1-yl)-3- fluorophenoxymethyl]-5-methylphenoxy]- propionate
• Step B N-(2-fluoro-4-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide
• the filtrate from Step A was mixed with 9.74 g (0.0640 mole) of 3,4,5,6-tetrahydrophthalic anhydride, and the mixture was heated at reflux for approximately 64 hours. At the end of this period, the dark brown solution was poured over ice and extracted in succession with ethyl acetate and diethyl ether. The extracts were combined, washed with water, dried over anhydrous magnesium sulfate, and filtered. The solvents were evaporated under reduced pressure from the filtrate, leaving a dark brown oil as residue. This was placed on a silica gel column and eluted with methylene chloride/ethyl acetate (95/5).
• Step C Methyl 2-(5-chloro-2-formylphenoxy)propionate
• a mixture of 22.0 g (0.141 mole) of 4-chlorosalicylaldehyde, 30 g (0.22 mole) of anhydrous potassium carbonate, and 30.0 g (0.184 mole) of methyl 2-bromo-propionate in 120 mL of N,N-dimethylformamide was heated at 80°C for approximately 17 hours. At the end of that period, the reaction mixture was poured over ice and extracted successively with diethyl ether and ethyl acetate. The combined extracts were washed with water, dried over anhydrous magnesium sulfate, and filtered. The solvents were then evaporated under reduced pressure, leaving a residue weighing 20 g.
• Step H 1.0 g (0.0038 mole) of methyl 2-(5-chloro-2-hydroxymethylphenoxy)-propionate and 0.5 g (0.0042 mole) of thionyl chloride were reacted in 20 mL of methylene chloride. After purification, 0.88 g of methyl 2-(2-chloromethyl-5-chlorophenoxy)propionate was isolated as a yellow liquid. The NMR spectrum was consistent with the proposed structure.
• Step F Methyl 2-[2-[3-fluoro-4-(3,4,5,6-tetrahydro-1- phthalimidyl)phenoxymethyl]-5-chlorophenoxy]- propionate
• Step I 0.50 g (0.0019 mole) of N-(2-fluoro-4-hydroxyphenyl)-3,4,5,6-tetrahydrophthalimide, 0.88 g (0.0034 mole) of methyl 2-(2-chloromethyl-5-chlorophenoxy)propionate, and 0.39 g
• Step B N- (2-Fluoro-4-methoxyphenyl)-N'-ethoxycarbonylmethylurea
• N-2(2-fluoro-4-methoxyphenyl)-N'-ethoxycarbonylmethylurea was isolated from this mixture as a purple solid, m.p. 158-159°C.
• the organic phase of the filtrate was separated, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated from the filtrate under reduced
• Step C 1-(1-Methylethyl)-3-(2-fluoro-4-methoxyphpnyl)imidazolidin-2,4-dione
• Step D 1-(1-methylethyl)-3-(2-fluoro-4-hydroxyphenyl)imidazolidin-2,4-dione
• Step E Methyl 2-[2-[3-fluoro-4-[1-(1-methylethyl)- imidazolidin-2,4-dion-3-yl]phenoxymethyl]-5- chlorophenoxy]propionate
• Example 2 By the method of Example 1, Step I, 0.60 g (0.0024 mole) of 1-(1-methylethyl)-3-(2-fluoro-4-hydroxyphenyl)imidazolidin-2,4-dione, 1.24 g (0.0048 mole) of methyl 2-(2-chloromethyl-5-chlorophenoxy)propionate (Example 2, Step E), and 0.5 g (0.0036 mole) of
• Step A 4-Fluorophenylmethyl 3-fluoro-4-nitrophenyl ether
• Step B 4-Fluorophenylmethyl 4-amino-3-fluorophenyl ether
• Step C 4-(4-Fluorophenylmethoxy)-2-fluorophenyl
• reaction mixture was stirred for one hour at room temperature and then at reflux for approximately seventeen hours.
• the toluene was removed by distillation, leaving 7.10 g of 4-(4-fluorophenylmethoxy)-2-fluorophenyl isocyanate.
• Step D 1-[4-(4-Fluorophenylmethoxy)-2-fluorophenyl]- 1,4-dihydro-5H-tetrazol-5-one
• Step E 1-[4-(4-Fluorophenylmethoxy)-2-fluorophenyl]- 1,4-dihydro-4-(3-fluoropropyl)-5H-tetrazol-5- one
• Step F 1-(2-Fluoro-4-hydroxyphenyl)-1,4-dihydro-4-(3- fluoropropyl)-5H-tetrazol-5-one
• Step G Methyl 2-[2-[4-[1,4-dihydro-4-(3-fluoropropyl)-5H-tetrazol-5-on-1-yl]-3-fluorophenoxymethyl]-5-methylphenoxy]propionate
• Example 1 By the method Example 1, Step I, 0.85 g (0.0033 mole) of 1-(2-fluoro-4-hydroxyphenyl)-1,4-dihydro-4-(3-fluoropropyl)-5H-tetrazol-5-one and 1.21 g (0.0050 mole) of methyl 2-(2-chloromethyl-5-methylphenoxy)-propionate (Example 1, Step H) were reacted in the presence of 0.70 g (0.0050 mole) of anhydrous potassium carbonate in 60 mL of N,N-dimethylformamide, yielding 0.42 g of methyl 2-[2-[4-[1,4-dihydro-4-(3-fluoropropyl)-5H-tetrazol-5-on-1-yl]-3-fluorophenoxymethyl]-5-methylphenoxy]propionate as an oil.
• Step B 2-(2-Fluoro-4-methoxyphenyl)-4,5,6,7-tetrahydro-1H-indazol-3-one
• Step C 3-Chloro-2-(2-fluoro-4-methoxyphenyl)-4,5,6,7- tetrahydro-1H-indazole
• Step D 3-Chloro-2-(2-fluoro-4-hydroxyphenyl)-4,5,6,7- tetrahydroindazole
• Step E Methyl 2-[2-[4-(3-chloro-4,5,6,7-tetrahydroindazol-2-yl)-3-fluorophenoxymethyl]-5-chlorophenoxy]propionate
• Example 2 By the method of Example 1, Step I, 0.49 g (0.0016 mole) of 3-chloro-2-(2-fluoro-4-hydroxyphenyl)-4,5,6,7-tetrahydroindazole and 0.52 g (0.002 mole) of methyl 2-(2-chloromethyl-5-chlorophenoxy)propionate (Example 2, Step E) were reacted in the presence of 0.41 g (0.003 mole) of anhydrous potassium carbonate in 30 mL of N,N-dimethylformamide, yielding 0.64 g of methyl 2-[2-[4- (3-chloro-4,5,6,7-tetrahydroindazol-2-yl)-3-fluorophenoxymethyl]-5-chlorophenoxy]propionate as a syrup.
• a stirred flask containing 350 mL of acetic acid was heated to 80-85°C under a nitrogen atmosphere.
• To this flask was added 39.10 g (0.700 mole) of powdered iron, and this mixture was stirred for one hour.
• a solution of 4-isopropoxy-2-fluoronitrobenzene in 250 mL was added to the mixture dropwise.
• the reaction mixture was heated at 80-85°C for one hour. After being cooled below 40°C, the mixture was filtered, and the solvent was evaporated under reduced pressure, leaving a residue. This resi-due was dissolved in a mixture of water and diethyl ether.
• the organic layer was separated and was washed in succession with saturated aqueous solutions of sodium bicarbonate and sodium chloride. It was then dried over anhydrous magnesium sulfate, filtered through a short column of silica gel, and the solvent was evaporated under reduced pressure, leaving an impure residue which contained significant amounts of acetamide in addition to the desired product. This residue was suspended in 500 mL of 2N hydrochloric acid for one hour. The hydrochloric acid mixture was then extracted with diethyl ether, and the two phases were separated. Aqueous sodium hydroxide solution was added to the aqueous hydrochloride solution until it was basic. This basic solution was extracted with diethyl ether, and the extract was dried over anhydrous magnesium sulfate and filtered.
• a mixture of 5.92 g (0.035 mole) of 4-isopropoxy-2-fluoroaniline, 10.60 g (0.043 mole) of malonyldiurethane, and 41.02 g (0.500 mole) of sodium acetate was suspended in 1000 mL of water with vigorous stirring. To this suspension was added 25 mL of 12 N hydrochloric acid. The reaction mixture was cooled to 10°C, and, while this temperature was maintained, a solution of 2.42 g (0.035 mole) of sodium nitrite in 25 mL of water was slowly added. The reaction mixture was allowed to warm slowly to room temperature where it was stirred under a nitrogen atmosphere for approximately 16 hours. During this period a yellow solid formed and precipitated out.
• Step D 2-(4-Isopropoxy-2-fluorophenyl)-1,2,4- triazine-3,5-dion-6-carboxylic acid
• Step F 2-(4-Isopropoxy-2-fluorophenyl)-4-methyl- 1,2,4-triazine-3,5-dione
• Step G 2-(4-Hydroxy-2-fluorophenyl)-4-methyl-1,2,4- triazine-3,5,-dione
• Step H Methyl 2-[2-[4-(4-methyl-1,2,4-triazine-3,5- dion-2-yl)-3-fluorophenoxymethyl]-5-methyl- phenoxy]propionate
• Step I 0.47 g (0.002 mole) of 2-(4-hydroxy-2-fluorophenyl)-4-methyl-1,2,4-triazine-3,5-dione and 0.73 g (0.003 mole) of methyl 2-(2-chloromethyl-5-methylphenoxy)propionate were reacted in the presence of 0.41 g (0.003 mole) of anhydrous potassium carbonate in 30 mL of N,N-dimethylformamide, yielding 0.70 g of methyl 2-[2-[4-(4-methyl-1,2,4-triazine-3,5-dion-2-yl)-3-fluorophenoxymethyl]-5-methylphenoxy]propionate as a syrup.
• Step A 4-(4-Difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5(1H)-on-1-yl)-3-fluorophenylsulfonyl chloride
• Step B 4-(4-Difluoromethyl-4,5-dihydro-3-methyl- 1,2,4-triazol-5(1H)-on-1-yl)-3-fluorothiophenol
• reaction mixture was heated at 85°C for 45 minutes.
• Example 2 By the method of Example 1, Step I, 1.35 g (0.0049 mole) of 4-(4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-on-1-yl)-3-fluorothiophenol and 3.0 g (0.011 mole) of methyl 2-(2-chloromethyl-5-chlorophenoxy)propionate (Example 2, Step E) were reacted in the presence of 1.02 g (0.0074 mole) of anhydrous potassium carbonate in 75 mL of N,N-dimethylformamide, yielding 0.54 g of methyl 2- [2-[4-(4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-on-1-yl)-3-fluorophenylthiomethyl]-5-chlorophenoxy]propionate as a yellow syrup.
• Step F 827 g (0.060 mole) of 4-methylsalicylaldehyde and 11.15 g (0.073 mole) of methyl bromoacetate were reacted in the presence of 10.1 g (0.073 mole) of anhydrous potassium carbonate in 150 mL of acetone, yielding 11.47 g of methyl (2-formyl-5-methylphenoxy) acetate as a white solid, m. p. 63-64°C.
• the NMR was consistent with the proposed structure.
• Step G 11.27 g (0.054 mole) of methyl (2-formyl-5-methylphenoxy) acetate was reacted with 0.54 g (0.014 mole) of sodium borohydride and 0.10 g (0.0018 mole) of sodium methoxide in 30 mL of methanol, yielding 9.41 g of methyl ( 2-hydroxymethyl-5-methylphenoxy) acetate as a yellow oil.
• the NMR spectrum was consistent with the proposed structure.
• Step H 9.21 g (0.044 mole) of methyl (2-hydroxymethyl-5-methylphenoxy)acetate was reacted with 7.40 g (0.062 mole) of thionyl chloride and 5 drops of pyridine in 50 mL of methylene chloride, yielding 5.57 g of methyl (2-chloromethyl-5-methylphenoxy)acetate as an orange liquid.
• Example 1 By the method of Example 1, Step I, 2.0 g (0.0077 mole) of 1-(2-fluoro-4-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one (Example 1, Step E) and 3.53 g (0.0151 mole) of methyl (2-chloromethyl-5-methylphenoxy)acetate were reacted in the presence of 1.60 g (0.0116 mole) of anhydrous potassium carbonate in 40 mL of N,N-dimethylformamide, yielding 2.75 g of methyl [2-[4-(4-difluoromethyl-4,5-dihydro-3-methyl-l,2,4-triazol-5(1H)-on-1-yl)-3-fluorophenoxymethyl]-5-methylphenoxy]acetate.
• Step F By the method of Example 1, Step F, 10.0 g (0.0819 mole) of 3-hydroxybenzaldehyde and 16.0 g (0.0982 mole) of methyl 2-bromopropionate were reacted in the
• Step G 15.7 g (0.0761 mole) of methyl 2-(3-formylphenoxy)propionate, 0.76 g (0.020 mole) of sodium borohydride, and 0.10 g (0.00.-8 mole) of sodium irethoxide were reacted in 40 mL of methanol, yielding 15.6 g of methyl 2-(3-hydroxymethylphenoxy) propionate as a yellow liquid.
• the NMR and IR spectra were consistent with the proposed structure.
• Step H 1.98 g (0.0095 mole) of methyl 2-(3-hydroxymethylphenoxy)propionate and 1.24 g (0.0105 mole) of thionyl chloride were reacted in the presence of five drops of pyridine in 40 mL of methylene chloride, yielding 1.93 g of methyl 2-(3-chloromethylphenoxy)propionate as a yellow liquid.
• the NMR and IR spectra were consistent with the
• Example 1 3y the method of Example 1, Step I, 1.0 g (0.0038 mole) of 1-(2-fluoro-4-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one (Example 1, Step F) and 1.72 g (0.0076 mole) of methyl 2-(3-chloromethylphenoxy)propionate were reacted in the presence of 0.79 g (0.0057 mole) of anhydrous potassium carbonate in 25 mL of N,N-dimethylformamide, yielding 1.54 g of methyl 2-[3-[4-(4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-on-1-yl)-3-fluorophenoxymethyl]phenoxy]propionate.
• Step F By the method of Example 1, Step F, 10.0 g (0.0819 mole) of 4-hydroxybenzaldehyde and 16.4 g (0.0983 mole) of methyl 2-bromopropionate were reacted in the
• Step B Methyl 2-(4-hydroxymethylphenoxy)propionate
• Step G 11.1 g (0.0533 mole) of methyl 2-(4-formylphenoxy)propionate and 2.02 g (0.0533 mole) of sodium borohydride were reacted in methanol, yielding 9.31 g of methyl 2- (4-hydroxymethylphenoxy) propionate as a yellow oil.
• the NMR spectrum was consistent with the proposed structure.
• Example 1, Step I 0.50 g (0.0019 mole) of 1-(2-fluoro-4-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one (Example 1, Step 2) and 0.87 g (0.0038 mole) of methyl 2-(4-chloromethylphenoxy)propionate were reacted in the presence of 0.2 g of 1,4,7,10,13,16-hexaoxacyclooctadecane in 25 mL of N,N-dimethylformamide, yielding 0.80 g of methyl 2-[4-[4-(4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-on-1-yl)-3-fluorophenoxymethyl]phenoxy]propionate as a colorless oil that solidified upon standing, m.p.
• Step I 1.71 g (0.010 mole) of 3-fluoro-4-nitrophenol and 2.85 g (0.011 mole) of methyl 2-(2-chloromethyl)5-methylphenoxy)propionate were reacted in the prer 3 of 1.66 g (0.012 mole) of anhydrous potassium carbonate in 100 mL of N,N-di- methyIformamide, yielding 3.55 g of methyl 2-[2-(3- fluoro-4-nitrophenoxymethyl)-5-methylphenoxy]propionate as a yellowish solid, m.p. 92-94°C.
• the NMR and IR spectra were consistent with the proposed structure.
• Step B Methyl 2-[2-(4-amino-3-fluorophenoxymethyl)-5- methylphenoxy]propionate
• Step A 3.35 g (0.0091 mole) of methyl 2-[2-(3-fluoro-4-nitrophenoxymethyl)-5-methylphenoxy]propionate was reacted with 2.80 g (0.050 mole) of powdered iron in 100 mL of acetic acid, yielding 1.86 g of methyl 2-[2-(4-amino-3-fluorophenoxymethyl)-5-methylphenoxy]propionate as an amber syrup.
• the NMR and IR spectra were consistent with the
• Step A 1-Methyl-3-(4-methoxyphenyl)-6- trifluoromethyl-2,4(1H,3H)-pyrimidinedione
• a flask was placed 8.27 g (0.207 mole) of a 60% suspension of sodium hydride in mineral oil. The mineral oil was removed by washing the sodium hydride twice with heptane. To the flask was then added 300 mL of tetrahydrofuran. This suspension was cooled to -20°C at which it was maintained during the dropwise addition of 37.9 g (0.207 mole) of 3-amino-4,4,4- trifluorocrotonate. This mixture was allowed to stir for 10 minutes before the dropwise addition of 30.83 g (0.207 mole) of 4-methoxyphenyl isocyanate was
• reaction mixture was heated at reflux for approximately 16 hours. At the conclusion of this period the reaction mixture was cooled to ambient temperature, and 28.56 g (0.207 mole) of potassium carbonate and 58.75 g (0.228 mole) of methyl iodide were added to it. The reaction mixture was then heated at reflux for seven hours. At the conclusion of this period the reaction mixture was cooled, and diethyl ether and water were added to it. The aqueous phase was separated from the organic phase. The latter was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, leaving a residue.
• Step B 1-Methyl-3-(4-hydroxyphenyl)-6- trifluoromethyl-2,4(1H,3H)-pyrimidinedione
• 25.88 g 0.086 mole
• 2-methyl-3-(4-methoxyphenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione was added dropwise 258 mL
• Example 1 By the method of Example 1, Step I, 0.7 g (0.0029 mole) of methyl 2-(2-chloromethyl-5-methylphenoxy)-propionate (Example 1, Step H), 0.30 g (0.0011 mole) of 1-methyl-3-(4-hydroxyphenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, and 0.22 g (0.0016 mole) of potassium carbonate were reacted in 80 mL of N,N-dimethylformamide, yielding 0.33 g of methyl 2-[2-[4- (1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedion-3-yl)phenoxymethyl]-5-methylphenoxy]propionate
• the 2-[ (4-heterocyclic-substituted-3-halophenoxy-methyl)phenoxy]alkanoates of this invention were tested in pre- and postemergence evaluations using a variety of broadleaf and grasseous crops and weeds.
• Williams field corn (Zea mays var. Agway 425X), wheat (Triticum aestivum var. Wheaton), morningglory (Ipomea lacunosa or Ipomea hederacea), velvetleaf (AbutiIon theophrasti), green foxtail (Setaria viridis),
• a topping soil of equal portions of sand and sandy loam soil was placed uniformly on top of each flat to a depth of approximately 0.5 cm.
• Flats for postemergence testing were prepared in the same manner, except that they were planted 8-12 days prior to the preemergence flats and were placed in a greenhouse and watered, thus allowing the seeds to germinate and the foliage to develop.
• a stock solution of the candidate herbicide was prepared by dissolving a predetermined weight of the compound in 20 ml of water/acetone (50/50) containing 0.5% v/v sorbitan monolaurate.
• 0.21 g of candidate herbicide was dissolved in 20 ml of the aqueous acetone to prepare the stock solution.
• a 1.0 mL portion of stock solution was diluted with water/acetone (50/50) to 35 ml, the volume required for a spray volume of 1000 L/ha. The remaining stock solution was then used to prepare spray solutions for other application rates.
• the spray solution (35 ml) was then sprayed on the four flats simultaneously, i.e., to the surface of the soil of the preemergence flats and to the emerged foliage of the postemergence flats. All flats were placed in the greenhouse, but only the preemergence flats were watered immediately. The foliage of the postemergence flats was kept dry for 24 hours, after which regular watering commenced. Phytotoxicity data, taken as percent control, were recorded 17-21 days after the chemical was applied.
• Percent control was determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science,” 2nd ed., B. Truelove, Ed.; Southern Weed Science Society; Auburn University, Auburn, Alabama, 1977.
• the rating system is as follows:
• the active compounds are formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application.
• the present herbicidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.
• herbicidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of vegetation is desired.
• Thes ⁇ formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
• Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns.
• a typical dust formulation useful herein is one containing 1.0 part or less of the herbicidal compound and 99.0 parts of talc.
• Wettable powders also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant.
• the wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid.
• Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate
• a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently
• additional wetting agent and/or oil will be added to the tank mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.
• ECs emulsifiable concentrates
• ECs emulsifiable concentrates
• ECs emulsifiable concentrates
• these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.
• the percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
• Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water.
• Flowables like ECs, may include a small amount of a surfactans, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition.
• flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
• Typical wetting, dispersing, or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide.
• the surface-active agent when used, normally comprises from 1 to 15% by weight of the composition.
• compositions include suspensions of the active ingredient in a relatively non-volatile liquid such as water, corn oil, kerosene, propylene glycol, or other suitable liquid carrier.
• Still other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents.
• Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy.
• Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freon fluorinated hydrocarbons, may also be used.
• Water-soluble or water-dispersible granules are also useful formulations for herbicidal application of the present compounds.
• Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible.
• the soluble or dispersible granular formulations described in U.S. patent No. 3,920,442 are useful with the present herbicidal compounds.
• the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc. may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
• the active herbicidal compounds of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture.
• an effective amount and concentration of the active compound is of course employed; the amount may be as low as, e.g. about 10 to 100 g/ha, preferably about 30 to 60 g/ha.
• higher application rates e.g., four times the greenhouse testing rates mentioned above may be employed.
• the active herbicidal compounds of this invention may be used in combination with other herbicides, e.g. they may be mixed with, say, a lesser, equal, or larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine (diethatyl ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2, 2-dioxide
• chloroacetanilide herbicides such as 2-chloro
• triazine herbicides such as 6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine(atrazine), and 2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino-2-methylpropamenitrile (cyanazine); dinitroaniline herbicides such as 2,6-dinitro-N,N,-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin); aryl urea herbicides such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) and N,N-dimethyl-N'-[3- (trifluoromethyl)phenyl] urea (fluometuron); and 2-[(2-chlorophenyl)methyl]-4,4-dimethyl-3-isox
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 85
• Soybean 10 0 60 0
• Morningglory 70 90 100 70
• Morningglory 100 90 95 80
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 95 100 85 100 Chickweed 100 100 90 100
• Morningglory 100 100 100 95
• Morningglory 80 100 100 100 100 100 100
• Morningglory 80 100 95 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Soybean 100 100 100 95
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 95 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 60 100 100 100 100 100 100 100
• Morningglory 95 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 95
• Morningglory 50 100 0 0
• Morningglory 100 100 85 100
• Morningglory 80 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Soybean 100 100 90 90
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 100 100 100 100 100 100 100
• Morningglory 100 100 40 80
• Morningglory 100 100 100 100 100 100 100 100 100

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• 1992
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